Heat transfer composition

ABSTRACT

A composition comprising a heat transfer portion and a lubricating portion, wherein the lubricating portion comprises one or more compounds according to formula (I) of the present disclosure, wherein W is H; Y is independently selected from the group consisting of F, Cl, Br and I; Z is independently selected from the group consisting of H, OH, (CW2)PCW3, CY3, OCW3, O(CW2)pCW3, OCW((CY2)mCY3)CWCW2, polyalkylene glycol and polyolester; n is an integer from 2 to 250; m is an integer from 0 to 3; and p is an integer from 0 to 9.

REFERENCE TO EARLIER FILED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/859,212, filed Apr. 27, 2020, which is a continuation of U.S. patentapplication Ser. No. 15/781,420, filed Jun. 4, 2018, which is a 371national phase of International Application No. PCT/GB2016/053850, filedDec. 7, 2016, which claims priority to GB Application No. 1521507.2,filed Dec. 7, 2015, the disclosures of all of which are incorporated byreference in their entireties.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to compositions, uses thereof and methodsfor preparing the same, wherein the composition comprises a heattransfer portion and a lubricating portion, wherein the lubricatingportion comprises a halogenated polyether.

BACKGROUND OF THE INVENTION

The listing or discussion of a prior-published document in thisspecification should not necessarily be taken as an acknowledgement thatthe document is part of the state of the art or is common generalknowledge.

Fluorocarbon-based compounds are currently used in a large number ofcommercial and industrial applications, such as propellants, blowingagents and heat transfer fluids. The interest in and use offluorine-based compounds, particularly (hydro)fluoroolefins, as heattransfer fluids has increased as new refrigerants are sought.

Dichlorodifluoromethane (refrigerant R-12) possesses a suitablecombination of refrigerant properties and was, for many years, the mostwidely used refrigerant. Due to international concern that fully andpartially halogenated chlorofluorocarbons, such asdichlorodifluoromethane and chlorodifluoromethane, were damaging theearth's protective ozone layer, there was general agreement that theirmanufacture and use should be severely restricted and eventually phasedout completely. The use of dichlorodifluoromethane was phased out in the1990's.

Chlorodifluoromethane (R-22) was introduced as a replacement for R-12because of its lower ozone depletion potential. Following concerns thatR-22 is a potent greenhouse gas, its use is also being phased out.R-410A and R-407 (including R-407A, R-407B and R-407C) have beenintroduced as a replacement refrigerant for R-22. However, R-22, R-410Aand the R-407 refrigerants all have a high global warming potential(GWP, also known as greenhouse warming potential).

1,1,1,2-tetrafluoroethane (refrigerant R-134a) was introduced as areplacement refrigerant for R-12. However, despite having a low ozonedepletion potential, R-134a has a GWP of 1430. It would be desirable tofind replacements for R-134a that have a lower GWP.

R-152a (1,1-difluoroethane) has been identified as an alternative toR-134a. It is somewhat more efficient than R-134a and has a greenhousewarming potential of 120. However the flammability of R-152a is judgedtoo high, for example to permit its safe use in mobile air conditioningsystems. In particular its lower flammable limit in air is too low, itsflame speeds are too high, and its ignition energy is too low.

(Hydro)fluoroolefins, particularly tetrafluoropropenes, have beenproposed as possible refrigerants for use in a variety of heat transferdevices.

Heat transfer fluids are often used in combination with lubricants, suchas in heating and refrigeration systems. Such lubricants are included inheat transfer compositions to ensure continued smooth operation of theheat transfer system.

It is necessary that lubricants used in heat transfer compositions arecompatible with the refrigerants in the compositions. The compatibilityof the lubricant and the refrigerant is predicated on a number offactors, such as a desire for at least partial miscibility at part ofthe operating temperature range, a low tendency to degrade or react inuse and appropriate viscosities for the application.

There is, therefore, a need for lubricants that can be used inconjunction with heat transfer fluids, both those currently used andthose proposed as replacement compositions. In particular, lubricantsare desired that are miscible with a wide range of heat transfer fluids,possess an appropriate viscosity, do not reduce the performance of heattransfer fluids and have low flammability; all in addition tosuccessfully functioning as a lubricant.

Lubricants with low flammability are particularly important for heattransfer fluids that are used in automobile air-conditioning, as suchcompositions are in danger of coming into contact with hot metalsurfaces of the engine.

DETAILED DESCRIPTION

The subject invention addresses the above and other deficiencies by theprovision of a composition comprising a heat transfer portion and alubricating portion, wherein the lubricating portion comprises acompound according to formula (I):

-   -   wherein    -   W is independently selected from the group consisting of H, F,        Cl, Br and I;    -   Y is independently selected from the group consisting of F, Cl,        Br and I;    -   Z is independently selected from the group consisting of H, OH,    -   (CW₂)_(p)CW₃, CY₃, OCW₃, O(CW₂)_(p)CW₃, OCW((CY₂)_(m)CY₃)CWCW₂,    -   polyalkylene glycol and polyolester;    -   n is an integer from 2 to 250;    -   m is an integer from 0 to 3; and    -   p is an integer from 0 to 9.

Such lubricants show excellent resistance to ignition, including whenexposed to hot surfaces.

Also provided by the invention is the use of such compositions describedabove as lubricants, for example, in heat transfer applications.

Further provided by the invention are methods of preparing suchcompositions described above.

Compositions of the Invention

In one aspect, the invention provides a composition comprising a heattransfer portion and a lubricating portion, wherein the lubricatingportion comprises a compound according to formula (I):

-   -   wherein    -   W is independently selected from the group consisting of H, F,        Cl, Br and I;    -   Y is independently selected from the group consisting of F, Cl,        Br and I;    -   Z is independently selected from the group consisting of H, OH,    -   (CW₂)_(p)CW₃, CY₃, OCW₃, O(CW₂)_(p)CW₃, OCW((CY₂)_(m)CY₃)CWCW₂,    -   polyalkylene glycol and polyolester;    -   n is an integer from 2 to 250;    -   m is an integer from 0 to 3; and    -   p is an integer from 0 to 9.

In an embodiment, Y is F or Cl, preferably F. W may be H, F or Cl.Preferably, W is H. Advantageously, m is an integer from 0 to 3,preferably 0 and n is an integer from 2 to 100, for example from 5 to20, preferably n is an integer from 10 to 20, e.g. 10, 11, 12, 13, 14,15, 16, 17, 18, 19 or 20.

Such lubricant/heat transfer component compositions show lowflammability, such as when sprayed onto hot surfaces or sprayed througha flame.

In an embodiment at least one of the Z derivatives is OH. Preferably,both Z derivatives are OH.

In another embodiment, at least one Z derivative may comprise apolyalkylene glycol. Alternatively, both Z derivatives may comprise apolyalkylene glycol (PAG). In both instances, the polyalkylene glycolmay be selected from the group consisting of poly(ethylene oxide) andpoly(propylene oxide), and mixtures thereof. In such embodiments, thePAG groups may be conjugated to the compound of formula (I) through theformation of an ester bond between a hydroxyl end-capping group offormula (I) (i.e., Z═OH) with a carboxylic acid end-capped PAG.

In a further embodiment, the Z derivatives may, independently, be analkyl or alkoxy group containing from 1 to 10 carbon atoms.

In an embodiment, both Z derivatives may be the same. Alternatively,both Z derivatives may be different.

In an embodiment, the weight percentage of the lubricating portion inthe total composition of the invention is 1-30%, preferably 1-10%, morepreferably 1-5%.

In an embodiment of the invention, the compound of formula (I) is acompound of formula (II):

In an alternative embodiment of the invention, the compound of formula(I) is a compound of formula (III):

In an embodiment of the invention, the PAG group of Formula (III) isconnected to the polymer backbone via an ester linkage. In anotherembodiment of the invention, the PAG group of Formula (III) is connectedto the polymer backbone via an ether linkage.

In an embodiment of the invention, the composition may comprise at leasttwo different compounds of formula (I). In such instances, the value ofn may be the same for the at least two compounds of formula (I).Alternatively, the value of n may be different for the at least twocompounds of formula (I).

In an embodiment of the invention, the lubricating portion of thecomposition may have a kinematic viscosity of from about 5 to about 250cSt at 40° C. Advantageously, the lubricating portion has a kinematicviscosity of from about 20 to about 100 cSt at 40° C., such as fromabout 30 to about 70 cSt, for example, from about 30 to about 60 cSt.

Preferably, the heat transfer portion comprises one or more compoundsselected from the group of (hydro)fluoroolefins (HFOs),hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs),hydrochlorofluorocarbons (HCFCs) and hydrocarbons.

Advantageously, the heat transfer portion may comprise one or morecompounds selected from the group of 1,3,3,3-tetrafluoropropene(R-1234ze), 2,3,3,3-tetrafluoropropene (R-1234yf),3,3,3-trifluoropropene (R-1243zf), 1,1,1,2-tetrafluoroethane (R-134a),1,1-difluoroethane (R-152a), difluoromethane (R-32), fluoroethane(R-161), pentafluoroethane (R-125), 1,1,2,2-tetrafluoroethane (R-134),propane, propylene, carbon dioxide, 1,1,1,3,3-pentafluoropropane(R-245fa), 1,1,1,3,3,3-hexofluoropropane (R-236fa),1,1,1,2,3,3,3-heptafluoropropane (R-227ea), 1,1,1-trifluoroethane(R-143a), n-butane, iso-butane and 1,1,1,3,3-pentafluorobutane(R-365mfc), 1,1,2-trifluoroethylene (R-1123), 1,1-difluoroethylene(R-1132a), 1,1,1,4,4,4-hexafluorobutene (R1336mzz), such as R-1234ze,R-1234yf, R-1243zf, R-134a, R-152a and R-32.

For the avoidance of doubt, it is to be understood that where a compoundmay exist as one of two configurational isomers, e.g. cis and transisomers around a double bond, the use of the term without an isomerdesignation (e.g. R-1234ze) is to refer to either isomer.

Conveniently, the heat transfer portion comprises tetrafluoropropenes.Preferably, the heat transfer portion comprises R-1234ze, even morepreferably the heat transfer portion comprises R-1234ze(E).Advantageously, the heat transfer composition comprises R-1234yf.

Advantageously, compositions of the invention are less flammable than acomposition comprising the same heat transfer portion combined with apolyalkylene glycol (PAG) and/or a polyol ester (POE) based lubricant.

In an embodiment, the composition of the invention is miscible withexisting polyalkylene glycol, polyalkylene glycol ester and polyol esterlubricating oils.

In an embodiment, the compounds comprising the lubricating portioncomprise carbon, hydrogen and oxygen, with a ratio of oxygen to carbonsufficient to provide a degree of miscibility with the heat transferportion, such as when the lubricating portion is added to the heattransfer portion in a proportion of from about 1 to 30 wt %, preferably1 to 10 wt % and even more preferably 1 to 5 wt % of the totalcomposition, the mixture has one liquid phase. Preferably, the mixturehas one liquid phase when 1 to 20 wt % of the lubricating portion ispresent in the composition. Even more preferably, the composition is oneliquid phase regardless of the proportions of the heat transfer portionto the lubricating portion. This solubility or miscibility preferablyexists at all normal operating temperatures. For example, the solubilityor miscibility exists at at least one temperature between −100° C. and+100° C., preferably at at least one temperature between −75° C. and+75° C. and even more preferably, at at least one temperature between−50° C. and +50° C. Advantageously, the solubility or miscibility existsover all temperature ranges wherein the composition is in the liquidphase.

Conveniently, the compositions of the invention are less flammable thanthe heat transfer portion alone.

Preferably, the composition of the invention has a lowest temperature ofignition of about 500° C. or greater, such as 510° C., 520° C., 530° C.,540° C., 550° C., 560° C., 570° C., 580° C., 590° C., preferably about600° C. or greater, for example 610° C., 620° C., 630° C. or 640° C.

In an embodiment, the composition of the invention may be non-flammable.

Flammability may be determined in accordance with ASHRAE Standard 34incorporating the ASTM Standard E-681 with test methodology as perAddendum 34p dated 2004, the entire content of which is incorporatedherein by reference.

Conveniently, the Global Warming Potential (GWP) of the compositions ofthe invention may be less than about 3500, 3000, 2500 or 2000. Forinstance, the GWP may be less than 2500, 2400, 2300, 2200, 2100, 2000,1900, 1800, 1700, 1600 or 1500. The GWP of the compositions of theinvention preferably is less than 1400, 1300, 1200, 1100, 1000, 900,800, 700, 600 or 500.

Preferably, the compositions of the invention have zero or near zeroozone depletion.

In an embodiment, the compositions of the invention have improved heattransfer properties than the heat transfer fluid alone.

Without wishing to be bound by theory, it is believed that compounds offormula (I) may further act as heat transfer agents and thereforeincrease the heat transfer properties of the compositions of theinvention.

Advantageously, the composition further comprises a stabiliser.

Preferably the stabiliser is selected from group consisting ofdiene-based compounds, phosphates, phenol compounds and epoxides, andmixtures thereof.

Conveniently, the composition further comprises an additional flameretardant.

Preferably, the flame retardant is selected from the group consisting oftri-(2-chloroethyl)-phosphate, (chloropropyl) phosphate,tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate,diammonium phosphate, various halogenated aromatic compounds, antimonyoxide, aluminium trihydrate, polyvinyl chloride, a fluorinatediodocarbon, a fluorinated bromocarbon, trifluoro iodomethane,perfluoroalkyl amines, bromo-fluoroalkyl amines and mixtures thereof.

In an embodiment, the composition of the invention may be comprisedwithin a lubricant composition in a proportion of at least 10 to 90 wt%, preferably in a proportion of 10 to 75 wt %, such as 10, 20, 30, 40or 50 wt %.

The invention also provides a heat transfer device containing acomposition of the invention and/or the use of a composition of theinvention in a heat transfer device.

In an embodiment, the heat transfer device is a refrigeration device.

Conveniently, the heat transfer device is selected from the groupconsisting of automotive air conditioning systems, residential airconditioning systems, commercial air conditioning systems, residentialrefrigerator systems, residential freezer systems, commercialrefrigerator systems, commercial freezer systems, chiller airconditioning systems, chiller refrigeration systems, and commercial orresidential heat pump systems.

Preferably, the heat transfer device contains a compressor.

According to a further aspect of the invention, there is provided amethod of cooling an article, which comprises condensing a compositionof the invention and thereafter evaporating the composition in thevicinity of the article to be cooled.

According to an another aspect of the invention, there is provided amethod for heating an article, which comprises condensing a compositionof the invention in the vicinity of the article to be heated andthereafter evaporating the composition.

According to a further aspect of the invention, there is provided amechanical power generation device containing a composition of theinvention.

Preferably, the mechanical power generating device is adapted to use aRankine Cycle or modification thereof to generate work from heat.

According to another aspect of the invention, there is provided a methodof retrofitting a heat transfer device comprising the step of removingan existing heat transfer fluid and introducing a composition of theinvention. Preferably, the heat transfer device is a refrigerationdevice. Advantageously, the heat transfer device is an air-conditioningsystem.

According to a further aspect of the invention, there is provided amethod of reducing the flammability of a composition by the addition ofa composition of the invention.

Methods of Preparation of Compositions of the Invention

Compositions of the invention may be prepared by mixing one or morecompounds of formula (I) with a heat transfer fluid.

Preferably, the heat transfer fluid comprises one or more compoundsselected from the group of (hydro)fluoroolefins (HFOs),hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs),hydrochlorofluorocarbons (HCFCs) and hydrocarbons.

Advantageously, the heat transfer fluid comprises one or more compoundsselected from the group of R-1234ze, R-1234yf, R-1243zf, R-134a, R-152a,R-32, R-161, R-125, R-134, propane, propylene, carbon dioxide, R-245fa,R-236fa, R-227ea, R-143a, R-1123, R-1132a, R1336mzz, n-butane,iso-butane and R-365mfc.

Conveniently, wherein the heat transfer fluid comprises one or morecompounds selected from the group of R-1234ze, R-1234yf, R-1243zf,R-134a, R-152a and R-32.

Preferably, the heat transfer fluid comprises R-1234ze.

Preferably, the heat transfer fluid comprises R-1234yf.

Uses of the Composition of the Invention

In an aspect, the composition of the invention may be used as a heattransfer agent. In an embodiment, when used as a heat transfer agent,the compositions of the invention may comprise at least two compoundsaccording to formula (I).

In another aspect, the compositions of the inventions may be used aslubricants. In an embodiment, the lubricant composition may comprise atleast two compounds according to formula (I).

The use of effective amounts of compounds according to formula (I) in alubricant composition or a heat transfer composition is advantageous dueto their thermal and mechanical stability, lubricity, viscosity, pourpoint, anti-oxidation and anti-corrosive properties.

Example

A compound according to the invention was synthesised by the followingmethod. A 450 mL Parr reactor was placed in an inert atmosphere inside aglove-box and 150 mL of 1,2-dimethoxyethane was added. 50 g (0.45 mol)of 3,3,3-trifluoropropylene oxide was then added along with 1.3 g (0.012mol) of potassium tert-butoxide. The reactor was then sealed, removedfrom the glove-box and connected to a stirrer. The reactor contents werethen stirred and heated to 90° C. for 5 days. The contents were thencooled and quenched with 200 mL of water. The resultingpolytrifluoropropylene oxide (PTFO) was extracted with diethyl ether anddried over a rotary evaporator.

The PTFO was tested to assess its flammability and/or combustibilityalone and mixed with fluorocarbon refrigerant compositions. It was foundthat the fluorinated species exhibited elevated combustion temperaturecompared to commercially available polyalkylene glycol (PAG) and polyolester (POE) lubricant materials.

Hot Manifold Testing

An assessment was made of the ease of ignition of the fluids when incontact with a hot metal surface, using the test apparatus and testmethod as described in ISO Standard ISO 20823:2003. In this testdroplets of the fluid were allowed to fall vertically downwards onto aninternally heated, cylindrical hot surface, inclined at a shallow angleto the horizontal, and which was additionally fitted with a horizontalgutter to trap liquid at one side of the cylindrical body. (The surfaceis hereinafter described as the “manifold”).

The temperature of the manifold was increased stepwise until ignitionwas observed. Observations on the character and vigour of ignition werealso recorded during each test. Five fluids of the invention, two PAGtype lubricants (Nippon Denso ND12 and Daphne FD46XG, ComparativeExamples 1 and 2, respectively) and one POE lubricant (Emkarate RL68H,comparative Example 3) were tested. A perfluorinated lubricant material(DuPont Krytox™ GPL150) was also tested as a comparative example. Theresults are tabulated below.

Highest temperature Lowest without ignition temperature with Fluid (°C.) ignition (° C.) Observations Example 676 — No sustained ignitionfound, though some brief flame flashes were observed on hot surfaceComparative 438 443 Immediate ignition; Example 1 burning liquidcollected Comparative 462 467 Immediate ignition; Example 2 burningliquid collected Comparative 628 633 Immediate ignition; Example 3 gasabove tray also ignited by droplets

The results clearly show a significant improvement in ignitionresistance offered by compounds according to the invention overconventional lubricants used in refrigeration technologies.

Preferences and options for a given aspect, feature or parameter of theinvention should, unless the context indicates otherwise, be regarded ashaving been disclosed in combination with any and all preferences andoptions for all other aspects, features and parameters of the invention.

Where a molecule, for example HFO-1234ze, may take the form of E and Zisomers, the general disclosure of that molecule is intended to referequally to both the E and Z isomers.

The invention is defined by the following claims.

The invention claimed is:
 1. A composition comprising a heat transfer portion and a lubricating portion, wherein the lubricating portion comprises one or more compounds according to formula (I):

wherein W is H; Y is independently selected from the group consisting of F, Cl, Br, and I; Z is independently selected from the group consisting of H, OH, (CW₂)_(p)CW₃, CY₃, OCW₃, O(CW₂)_(p)CW₃, OCW((CY₂)_(m)CY₃)CWCW₂, polyalkylene glycol, and polyolester; n is an integer from 2 to 250; m is an integer from 0 to 3; and p is an integer from 0 to
 9. 2. The composition according to claim 1, wherein Y is F or Cl.
 3. The composition according to claim 1, wherein n is an integer from 2 to
 100. 4. The composition according to claim 1, wherein m is
 0. 5. The composition according to claim 1, wherein p is 1 to
 6. 6. The composition according to claim 1, wherein Z is OH or comprises a polyalkylene glycol.
 7. The composition according to claim 6, wherein the polyalkylene glycol is selected from the group consisting of poly(ethylene oxide), poly(propylene oxide), and mixtures thereof.
 8. The composition according to claim 1, wherein at least one of the Z derivatives are not H or OH.
 9. The composition according to claim 1, wherein the composition comprises at least two different compounds of formula (I).
 10. The composition according to claim 1, wherein the lubricating portion has a kinematic viscosity at 40° C. of from about 5 to about 250 cSt.
 11. The composition according to claim 10, wherein the lubricating portion has a kinematic viscosity at 40° C. of from about 20 to 100 cSt.
 12. The composition according to claim 1, wherein the weight percentage of the lubricating portion in the composition is 1 to 30%.
 13. The composition according to claim 1, wherein the heat transfer portion comprises one or more compounds selected from the group consisting of (hydro)fluoroolefins (HFOs), hydrofluorocarbons (HFCs), chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrocarbons.
 14. The composition according to claim 1, wherein the heat transfer portion comprises one or more compounds selected from the group consisting of R-1234ze, R-1234yf, R-1243zf, R-134a, R-152a, R-32, R-161, R-125, R-134, propane, propylene, carbon dioxide, R-245fa, R-236fa, R-227ea, R-143a, n-butane, iso-butane, R-365mfc, R-1123, R-1132a, and R1336mzz.
 15. The composition according to claim 1, which is less flammable than the heat transfer fluid alone.
 16. The composition according to claim 1, which has an ignition temperature of about 500° C. or greater.
 17. The composition according to claim 1, which is non-flammable.
 18. The composition according to claim 1, further comprising a stabiliser and/or a flame retardant.
 19. The composition according to claim 18, wherein the stabiliser is selected from the group consisting of diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof.
 20. The composition according to claim 18, wherein the flame retardant is selected from the group consisting of tri-(2-chloroethyl)-phosphate, (chloropropyl) phosphate, tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate, diammonium phosphate, antimony oxide, aluminium trihydrate, polyvinyl chloride, a fluorinated iodocarbon, a fluorinated bromocarbon, trifluoro iodomethane, perfluoroalkyl amines, bromo-fluoroalkyl amines, and mixtures thereof.
 21. A heat transfer device containing a composition according to claim
 1. 22. The heat transfer device according to claim 21, which is selected from the group consisting of automotive air conditioning systems, residential air conditioning systems, commercial air conditioning systems, residential refrigerator systems, residential freezer systems, commercial refrigerator systems, commercial freezer systems, chiller air conditioning systems, chiller refrigeration systems, and commercial or residential heat pump systems.
 23. A method of cooling an article, which comprises condensing a composition according to claim 1 and thereafter evaporating the composition in the vicinity of the article to be cooled.
 24. A method for heating an article, which comprises condensing a composition according to claim 1 in the vicinity of the article to be heated and thereafter evaporating the composition.
 25. A mechanical power generation device containing a composition according to claim
 1. 26. The mechanical power generating device according to claim 25, which is adapted to use a Rankine Cycle or modification thereof to generate work from heat.
 27. A method of retrofitting a heat transfer device comprising the step of removing an existing heat transfer fluid and introducing a composition according to claim
 1. 28. The method according to claim 27, wherein the heat transfer device is a refrigeration device.
 29. The method according to claim 28, wherein the heat transfer device is an air-conditioning system. 